1-azabutadienes and fungicides containing these compounds

ABSTRACT

1-Azabutadienes of the formula ##STR1## where R 1  and R 2  are each phenyl, biphenyl, naphthyl or pyridyl, and these radicals may be substituted, or are each alkyl which is unsubstituted or substituted, R 3  is substituted or unsubstituted phenyl or a radical OR 4 , where R 4  is hydrogen, alkyl or an aromatic or aliphatic acyl group, or R 3  is a radical NHR 5 , where R 5  is hydrogen, substituted or unsubstituted phenyl, or the carbamide group, and fungicidal agents containing these compounds.

The present invention relates to 1-azabutadienes and fungicides containing these compounds.

We have found novel 1-azabutadienes of the formula I ##STR2## where R¹ and R² are identical or different and are each phenyl, biphenyl, naphthyl or pyridyl, and these radicals may be monosubstituted to trisubstituted by halogen, nitro, phenoxy, amino, haloalkyl, alkyl or alkoxy, each of 1 to 4 carbon atoms, or are each straight-chain or branched C₁ -C₈ -alkyl which is unsubstituted or substituted by unsubstituted or substituted phenyl, and

R³ is unsubstituted or substituted phenyl or a radical OR⁴, where

R⁴ is hydrogen, straight-chain or branched C₁ -C₆ -alkyl or an aromatic or aliphatic acyl group, or R³ is a radical NHR⁵, where

R⁵ is hydrogen, unsubstituted or substituted phenyl or the carbamide group CONH₂, which have a very good fungicidal action.

In formula I, R¹ and R² independently of one another are each, for example, 1-naphthyl, 2-naphthyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, p-biphenyl, phenyl, halophenyl, e.g. 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2-bromophenyl, 3-bromophenyl or 4-bromophenyl, halo-C₁ -C₄ -alkylphenyl, e.g. 2-trifluoromethylphenyl, 3-trifluoromethyllphenyl or 4-trifluoromethylphenyl, C₁ -C₄ -alkylphenyl, or 2-methylphenyl, 3-methylphenyl or 4-methylphenyl, C₁ -C₄ -alkoxyphenyl, e.g. 2-methoxyphenyl, 3-methoxyphenyl or 4-methoxyphenyl, 2,3-dichlorophenyl, 2,4-dichlorophenyl, 2,5-dichlorophenyl, 2,6-dichlorophenyl, 2-chloro-6-fluorophenyl, 2-chloro-4-fluorophenyl, 2-fluoro-4-chlorophenyl, 2,4-dimethylphenyl, 2,6-dimethylphenyl or 2,4,6-trimethylphenyl or C₁ -C₈ -alkyl, in particular C₁ -C₄ -alkyl, e.g. methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl or 2,2-dimethylpropyl, benzyl, halobenzyl, e.g. 4-chlorobenzyl or 4-fluorobenzyl, C₁ -C₄ -alkylbenzyl, e.g. 4-methylbenzyl, 2-chlorobenzyl, 2-fluorobenzyl, 2-methylbenzyl or 2-phenylethyl, halophenylethyl, e.g. 4-chlorophenylethyl or 4-fluorophenylethyl, or 3-phenylpropyl.

Particularly preferred compounds are those in which R¹ is an unsubstituted or substituted phenyl ring, for example phenyl or halophenyl, e.g. 4-chlorophenyl, 4-fluorophenyl, 2-chlorophenyl or 2-fluorophenyl, and R² is 2,2-dimethylpropyl or 3,3-dimethylbutyl or unsubstituted or substituted phenyl, for example phenyl or halophenyl, e.g. 4-chlorophenyl, 4-fluorophenyl, 2-chlorophenyl or 2-fluorophenyl.

R³ is, for example, hydroxyl or the group OR⁴, where R⁴ is an aliphatic or aromatic acyl radical, for example C₁ -C₄ -alkyl-CO, acetyl, propionyl, butyryl, benzoyl or halobenzoyl, e.g. 4-chlorobenzoyl, or unsubstituted or substituted C₁ C₆ -alkyl, in particular C₁ -C₄ -alkyl, such as methyl, ethyl, propyl or butyl, benzyl or halobenzyl, or

R³ is a radical NHR⁵, where R⁵ is hydrogen, the carbamide group CONH₂ or unsubstituted or substituted phenyl, for example phenyl or nitrophenyl, e.g. 4-nitrophenyl or 2,4-dinitrophenyl.

Finally, R³ is furthermore unsubstituted or substituted phenyl, for example phenyl, halophenyl, such as 4-chlorophenyl or 4-bromophenyl, or C₁ C₄ -alkylphenyl, such as 4-methylphenyl.

R³ is particularly preferably hydroxyl and derivatives derived therefrom which can be obtained by alkylation or acylation.

1-Azabutadienes of the formula I can be obtained, for example, by reacting an aldehyde II ##STR3## with a compound of the formula H₂ N-R³ in the presence or absence of a catalyst and of a suitable solvent. Waterremoving agents, such as molecular sieves, such as magnesium sulfate, sodium sulfate or calcium chloride, may be used as catalysts, as well as acids, such as sulfuric acid, hydrochloric acid or acetic acid, or basic compounds, such as sodium hydroxide, potassium hydroxide, potassium carbonate or potassium acetate. Examples of solvents are lower alcohols, such as methyl alcohol or ethyl alcohol, and their mixtures with water, as well as propyl alcohol, isopropyl alcohol, butanol, sec-butanol or tert-butanol, ketones, such as acetone, ethers, such as diethyl ether, tetrahydrofuran or methyl tert-butyl ether, and methylene chloride, aromatic hydrocarbons, such as toluene or xylene, and dimethylformamide and dimethyl sulfoxide.

Method 1

5,5-Dimethyl-2-formyl-1-(p-chlorophenyl)-hex-2-ene (compound 136a)

79 g (0.79 mol) of 3,3-dimethylbutyraldehyde are added to a solution of 10.5 g of 50% strength by weight aqueous NaOH in 500 ml of methanol, after which 123 g (0.73 mol) of p-chlorodihydrocinnamaldehyde are added dropwise at 34° C. The mixture is stirred for one hour and then neutralized with dilute sulfuric acid, the solution is evaporated down and the residue is then subjected to fractional distillation.

Bp. 119°-122° C/0.01 mbar, yield 115.9 g (59% of theory)

Method 2

1-(o-Chlorophenyl)-3-(p-fluorophenyl)-2-formylprop-1-ene

71.7 g (0.51 mol) of 2-chlorobenzaldehyde are added to a solution of 4 g of 50% strength sodium hydroxide solution in 300 ml of methanol while cooling, at a rate such that the temperature does not exceed 20° C. 70.0 g (0.46 mol) of p-fluorodihydrocinnamaldehyde are then added dropwise at 25°-30° C. in the course of 4 hours. Stirring is continued for one hour at 30° C., the mixture is neutralized with dilute sulfuric acid and evaporated down and the residue is distilled.

Bp. 164°-184° C./0.3 mbar; yield 97.8 g (77% of theory)

Method 3

4,4-Dimethyl-2-formyl-1-(p-chlorophenyl)-pent-1-ene (compound 63a)

134 g (0.95 mol) of 4-chlorobenzaldehyde are added to a solution of 15.8 g of 50% strength sodium hydroxide solution in 500 ml of methanol, after which 90 g (0.79 mol) of 4,4-dimethylpentanal are added dropwise at 35° C. in the course of 3 hours. Stirring is carried out for three hours, after which the mixture is neutralized with dilute sulfuric acid and evaporated down and the residue is distilled.

Bp. 117°-120° C./0.4 mbar; yield 83.5 g (39% of theory)

PREPARATION EXAMPLE 1 compound 136

4.2 g (0.06 mol) of hydroxylammonium hydrochloride, dissolved in a methanol/water mixture, and 4.1 g (0.03 mol) of potassium carbonate were added to a solution of 7.5 g (0.03 mol) of the aldehyde from method 1 in 100 ml of methanol. After a reaction time of one hour at 25° C., the mixture was evaporated down and the product was extracted with methylene chloride. Yield 6.8 g (85% of theory), mp. 78° C.

PREPARATION EXAMPLE 2 compound 139

5.0 g (0.019 mol) of the oxime from Example 1 were dissolved in 50 ml of tetrahydrofuran, and 3.0 g of pyridine and 0.1 g of 4-(N,N-dimethylamino)-pyridine were added, followed by the dropwise addition, at 50° C., of 2.2 g (0.03 mol) of acetyl chloride dissolved in 20 ml of tetrahydrofuran. After a reaction time of 72 hours at 25° C., the mixture was evaporated down, the residue was taken up with methyl tert-butyl ether, the solution was washed with dilute NaHCO₃ solution and the organic phase was dried and evaporated down.

Yield 4.3 g (78% of theory), IR bands: 2958, 1769, 1492, 1366, 1204 cm⁻³

The following compounds can be prepared in a similar manner.

                                      TABLE 1                                      __________________________________________________________________________      ##STR4##                                                                      No. R.sup.1 R.sup.2   R.sup.3      m.p. (°C.)/IR                        __________________________________________________________________________                                        (cm.sup.-1)/(NMR)                           1   n-C.sub.3 H.sub.7                                                                      phenyl    OH                                                       2   n-C.sub.3 H.sub.7                                                                      4-ClPh    OH                                                       3   n-C.sub.3 H.sub.7                                                                      4-FPh     OH            91-93                                      4   n-C.sub.3 H.sub.7                                                                      4-FPh     NHCONH.sub.2 152                                         5   n-C.sub.3 H.sub.7                                                                      4-MePh    OH                                                       6   n-C.sub.3 H.sub.7                                                                      2-ClPh    OH                                                       7   n-C.sub.3 H.sub.7                                                                      2-FPh     OH                                                       8   n-C.sub.3 H.sub.7                                                                      2,4-Cl.sub.2 Ph                                                                          OH                                                       9   n-C.sub.3 H.sub.7                                                                      3-pyridine                                                                               OH           118-121                                     10  n-C.sub.3 H.sub.7                                                                      3-pyridine                                                                               OMe                                                      11  n-C.sub.3 H.sub.7                                                                      3-pyridine                                                                               OEt                                                      12  n-C.sub.3 H.sub.7                                                                      3-pyridine                                                                               OCOMe        0.9-2.6(9, m); 2.2(3, s);                                                      6.8-8.7(6, m)                               13  n-C.sub.3 H.sub.7                                                                      3-pyridine                                                                               OCOPh        0.9-2.7(9, m);                                                                 6.8-8.7(11, m)                              14  n-C.sub.3 H.sub.7                                                                      4-pyridine                                                                               OH                                                       15  n-C.sub.3 H.sub.7                                                                      2-pyridine                                                                               OH                                                       16  n-C.sub.3 H.sub.7                                                                      1-naphthyl                                                                               OH                                                       17  n-C.sub.3 H.sub.7                                                                      2-naphthyl                                                                               OH                                                       18  n-C.sub.3 H.sub.7                                                                      4-biphenyl                                                                               OH                                                       19  n-Bu    phenyl    OH                                                       20  n-Bu    4-ClPh    OH                                                       21  n-Bu    4-FPh     OH                                                       22  n-Bu    4-MePh    OH                                                       23  n-Bu    2-ClPh    OH                                                       24  n-Bu    2-FPh     OH                                                       25  n-Bu    2,4-Cl.sub.2Ph                                                                           OH                                                       26  n-Bu    3-pyridine                                                                               OH                                                       27  t-Bu    Ph        OH                                                       28  t-Bu    4-ClPh    OH           108-110                                     29  t-Bu    4-ClPh    OMe                                                      30  t-Bu    4-ClPh    OEt          2959, 1490, 1092, 1055                      31  t-Bu    4-ClPh    OCOMe        2961, 1769, 1490, 1203                      32  t-Bu    4-ClPh    OCOPh                                                    33  t-Bu    4-ClPh    NHPh                                                     34  t-Bu    4-FPh     OH                                                       35  t-Bu    4-FPh     OCOMe                                                    36  t-Bu    4-MePh    OH                                                       37  t-Bu    2-ClPh    OH                                                       38  t-Bu    2-FPh     OH                                                       39  t-Bu    2,4-Cl.sub.2Ph                                                                           OH                                                       40  t-Bu    3-pyridine                                                                               OH           178                                         41  t-Bu    3-pyridine                                                                               OCOMe        0.8-2.7(14, m); 6.9-8.7(6, m)               42  t-Bu    cyclohexyl                                                                               OH           88                                          43  t-Bu    cyclohexyl                                                                               OMe          2930, 2852, 1448, 1059                      44  t-Bu    cyclohexyl                                                                               OEt          2929, 2852, 1448, 1056                      45  t-Bu    cyclohexyl                                                                               OCOMe        2930, 2853, 1773, 1366, 1202                46  t-Bu    cyclohexyl                                                                               OCOPh        <50                                         47  t-Bu    cyclohexyl                                                                               NHPh         123                                         48  t-Bu    cyclohexyl                                                                               4-BrPh       2928, 2852, 1612, 1481, 825                 49  n-pentyl                                                                               Ph        OH                                                       50  n-pentyl                                                                               4-ClPh    OH                                                       51  n-pentyl                                                                               4-FPh     OH                                                       52  n-pentyl                                                                               4-MePh    OH                                                       53  n-pentyl                                                                               2-ClPh    OH                                                       54  n-pentyl                                                                               2-FPh     OH                                                       55  n-pentyl                                                                               2,4-Cl.sub.2PH                                                                           OH                                                       56  n-pentyl                                                                               3-pyridine                                                                               OH           120                                         57  n-pentyl                                                                               3-pyridine                                                                               OMe          0.9-3.9(16, m); 6.5-8.6(6, m)               58  n-pentyl                                                                               3-pyridine                                                                               OEt          0.9-4.2(18, m); 6.5-8.6(6, m)               59  n-pentyl                                                                               3-pyridine                                                                               OCOMe        0.9-2.6(16, m); 6.4-8.7(6, m)               60  n-pentyl                                                                               3-pyridine                                                                               OCOPh        0.9-2.8(13, m); 6.7-8.7(11, m)              61  n-pentyl                                                                               3-pyridine                                                                               NHPh         0.9-2.7(13, m); 6.4-8.6(11, m)              62                                                                                  ##STR5##                                                                              Ph        OH                                                       63                                                                                  ##STR6##                                                                              4-ClPh    OH                                                       64                                                                                  ##STR7##                                                                              4-FPh     OH                                                       65                                                                                  ##STR8##                                                                              4-MePh    OH                                                       66                                                                                  ##STR9##                                                                              2-ClPh    OH                                                       67                                                                                  ##STR10##                                                                             2-FPh     OH                                                       68                                                                                  ##STR11##                                                                             2,4-Cl.sub.2Ph                                                                           OH                                                       69                                                                                  ##STR12##                                                                             3-pyridine                                                                               OH                                                       70  n-Hexyl Ph        OH                                                       71  n-Hexyl 4-ClPh    OH                                                       72  n-Hexyl 4-FPh     OH                                                       73  n-hexyl 4-MePh    OH                                                       74  n-hexyl 2-ClPh    OH                                                       75  n-hexyl 2-FPh     OH                                                       76  n-hexyl 2,4-Cl.sub.2Ph                                                                           OH                                                       77  n-hexyl 3-pyridine                                                                               OH                                                       78                                                                                  ##STR13##                                                                             Ph        OH                                                       79                                                                                  ##STR14##                                                                             4-ClPh    OH                                                       80                                                                                  ##STR15##                                                                             4-FPh     OH                                                       81                                                                                  ##STR16##                                                                             4-MePh    OH                                                       82                                                                                  ##STR17##                                                                             2-ClPh    OH                                                       83                                                                                  ##STR18##                                                                             2-FPh     OH                                                       84                                                                                  ##STR19##                                                                             2,4-Cl.sub.2Ph                                                                           OH                                                       85                                                                                  ##STR20##                                                                             3-pyridine                                                                               OH                                                       86  Ph      Ph        OH                                                       87  Ph      4-ClPh    OH                                                       88  Ph      4-FPh     OH                                                       89  Ph      4-MePh    OH                                                       90  Ph      2-ClPh    OH                                                       91  Ph      2-FPh     OH                                                       92  Ph      2,4-Cl.sub.2Ph                                                                           OH                                                       93  Ph      3-pyridine                                                                               OH                                                       94  Ph      n-Bu      OH                                                       95  Ph      t-Bu      OH                                                       96  Ph      n-pentyl  OH                                                       97  Ph                                                                                      ##STR21##                                                                               OH                                                       98  Ph                                                                                      ##STR22##                                                                               OMe                                                      99  Ph                                                                                      ##STR23##                                                                               OEt                                                      100 Ph                                                                                      ##STR24##                                                                               OCOMe                                                    101 Ph                                                                                      ##STR25##                                                                               OCOPh                                                    102 Ph                                                                                      ##STR26##                                                                               NHPh                                                     103 Ph                                                                                      ##STR27##                                                                                ##STR28##                                               104 4-ClPh                                                                                  ##STR29##                                                                               NHCONH.sub.2 0.9-4.1(13, m); 6.0-7.5(6, m)               105 Ph      n-hexyl   OH                                                       106 Ph                                                                                      ##STR30##                                                                               OH                                                       107 Ph                                                                                      ##STR31##                                                                               OMe                                                      108 Ph                                                                                      ##STR32##                                                                               OEt          2956, 2867, 1052, 698                       109 Ph                                                                                      ##STR33##                                                                               OCOMe        2956, 2866, 1770, 1366, 1204                110 Ph                                                                                      ##STR34##                                                                               OCOPh        2956, 2907, 1749, 1257, 1245                111 Ph                                                                                      ##STR35##                                                                               NHPh         2955, 2904, 2865, 1600, 1495                112 Ph      CH.sub.2CH.sub.2                                                                          ##STR36##   145-148                                     113 Ph                                                                                      ##STR37##                                                                               NHCOCH.sub.2 2955, 2907, 1692, 1582, 698                 114 Ph      CH.sub.2CH.sub.2Ph                                                                       OH           3026, 2925, 1495, 1452, 698                 115 Ph      CH.sub.2CH.sub.2Ph                                                                       OMe          2935, 1495, 1452, 1047, 698                 116 Ph      CH.sub.2CH.sub.2Ph                                                                       OEt          2931, 1495, 1453, 1051, 698                 117 Ph      CH.sub.2CH.sub.2Ph                                                                       OCOMe        3026, 1766, 1453, 1204, 700                 118 Ph      CH.sub.2CH.sub.2Ph                                                                       OCO Ph       1746, 1451, 1257, 1246, 700                 119 Ph      CH.sub.2CH.sub.2Ph                                                                       NHPh         3025, 1602, 1494, 1258, 697                 120 Ph      CH.sub.2CH.sub.2Ph                                                                        ##STR38##   144-146                                     121 Ph      CH.sub.2CH.sub.2Ph                                                                       NHCONH.sub.2 3463, 1693, 1582, 696                       122 4-ClPh  Ph        OH                                                       123 4-ClPh  4-ClPh    OH                                                       124 4-ClPh  4-FPh     OH           152-154                                     125 4-ClPh  4-FPh     OCH.sub.3    3.7-3.9(5, m); 6.8-7.9(10, m)               126 4-ClPh  4-FPh     OEt          1.1-4.2(7, m); 6.7-7.9(10, m)               127 4-ClPh  4-FPh     OCOMe        2.2-4.0(5, m); 7.0-8.2(10, m)               128 4-ClPh  4-FPh     OCOPh         88                                         129 4-ClPh  4-FPh     NHPh         142-144                                     130 4-ClPh  4-FPh                                                                                     ##STR39##   195-197                                     131 4-ClPh  4-FPh     NHCOCH.sub.2 163-164                                     132 4-ClPh  4-MePh    OH                                                       133 4-ClPh  2-ClPh    OH                                                       134 4-ClPh  2-FPh     OH                                                       135 4-ClPh  2,4-Cl.sub.2Ph                                                                           OH                                                       136 4-ClPh                                                                                  ##STR40##                                                                               OH            78                                         137 4-ClPh                                                                                  ##STR41##                                                                               OMe          2958, 2900, 1492, 1052, 797                 138 4-ClPh                                                                                  ##STR42##                                                                               OEt          0.9-4.1(16, m); 3.7(2, s);                                                     5.9-7.8(6, m)                               139 4-ClPh                                                                                  ##STR43##                                                                               OCOMe        2958, 1769, 1492, 1366, 1204                140 4-ClPh                                                                                  ##STR44##                                                                               OCOPh        2958, 1748, 1491, 1244, 707                 141 4-ClPh                                                                                  ##STR45##                                                                               NHPh         0.9-3.8(13, m); 5.8-7.4(11, m)              142 4-ClPh  CH.sub.2                                                                                  ##STR46##   154                                         143 4-ClPh  CH.sub.2  NHCONH.sub.2 118                                         144 4-ClPh                                                                                  ##STR47##                                                                               OCOOEt                                                   145 4-ClPh                                                                                  ##STR48##                                                                               OH                                                       146 4-ClPh                                                                                  ##STR49##                                                                               OMe                                                      147 4-ClPh                                                                                  ##STR50##                                                                               OEt                                                      148 4-ClPh                                                                                  ##STR51##                                                                               OCOMe                                                    149 4-ClPh                                                                                  ##STR52##                                                                               OCOPh                                                    150 4-ClPh                                                                                  ##STR53##                                                                               NHPh                                                     151 4-ClPh                                                                                  ##STR54##                                                                                ##STR55##                                               152 4-ClPh                                                                                  ##STR56##                                                                               NHCONH.sub.2                                             153 4-FPh   Ph        OH                                                       154 4-FPh   4-ClPh    OH                                                       155 4-FPh   4-FPh     OH                                                       156 4-FPh   4-MePh    OH                                                       157 4-FPh   2-ClPh    OH           3280, 1506, 1432, 1219                      158 4-FPh   2-ClPh    OCH.sub.3    1508, 1218, 977, 761, 532                   159 4-FPh   2-ClPh    OEt                                                      160 4-FPh   2-ClPh    OCOMe        2.1-3.9(5, m); 6.9-8.2(10, m)               161 4-FPh   2-ClPh    OCOPh        1691, 1510, 1213, 710                       162 4-FPh   2-ClPh                                                                                    ##STR57##   1508, 1235, 1036, 749                       163 4-FPh   2-ClPh                                                                                    ##STR58##                                               164 4-FPh   2-ClPh                                                                                    ##STR59##   1508, 1232, 1037, 758                       165 4-FPh   2-ClPh                                                                                    ##STR60##   1603, 1507, 1258, 751                       166 4-FPh   2-ClPh                                                                                    ##STR61##   188                                         167 4-FPh   2-ClPh    phenyl                                                   168 4-FPh   2-ClPh                                                                                    ##STR62##    78                                         169 4-FPh   2-ClPh    NHCONH.sub.2                                             170 4-FPh   2-ClPh    OCH.sub.2Ph                                              171 4-FPh   2-ClPh    OCOOEt                                                   172 4-FPh   2-FPh     OH                                                       173 4-FPh   2-FPh     OH                                                       174 4-FPh                                                                                   ##STR63##                                                                               OH           0.9-3.7(13, m); 5.3-7.8(6, m)               175 4-FPh                                                                                   ##STR64##                                                                               OMe          2958, 1508, 1224, 1051                      176 4-FPh                                                                                   ##STR65##                                                                               OEt          2959, 1508, 1223, 1052                      177 4-FPh                                                                                   ##STR66##                                                                               OCOMe        2958, 1769, 1509, 1222, 1204                178 4-FPh                                                                                   ##STR67##                                                                               OCOPh        2957, 1748, 1509, 1245, 708                 179 4-FPh                                                                                   ##STR68##                                                                               NHPh          70                                         180 4-FPh                                                                                   ##STR69##                                                                                ##STR70##   161                                         181 4-FPh                                                                                   ##STR71##                                                                               NHCONH.sub.2  53                                         182 4-FPh                                                                                   ##STR72##                                                                               phenyl                                                   183 4-FPh                                                                                   ##STR73##                                                                                ##STR74##   2958, 1507, 1481, 1222                      184 4-FPh                                                                                   ##STR75##                                                                               OH                                                       185 4-F Ph                                                                                  ##STR76##                                                                               OMe                                                      186 4-FPh                                                                                   ##STR77##                                                                               OEt                                                      187 4-FPh                                                                                   ##STR78##                                                                               OCOMe                                                    188 4-FPh                                                                                   ##STR79##                                                                               OCOPh                                                    189 4-FPh                                                                                   ##STR80##                                                                               NHPh                                                     190 4-FPh                                                                                   ##STR81##                                                                                ##STR82##                                               191 4-FPh                                                                                   ##STR83##                                                                               NHCONH.sub.2                                             192 2-ClPh  Ph        OH                                                       193 2-ClPh  4-ClPh    OH                                                       194 2-ClPh  4-FPh     OH                                                       195 2-ClPh  4-MePh    OH                                                       196 2-ClPh  2-ClPh    OH                                                       197 2-ClPh  2-FPh     OH                                                       198 2-ClPh  2,4-Cl.sub.2Ph                                                                           OH                                                       199 2-FPh   Ph        OH                                                       200 2-FPh   4-ClPh    OH                                                       201 2-FPh   4-FPh     OH                                                       202 2-FPh   4-MePh    OH                                                       203 2-F Ph  2-ClPh    OH                                                       204 2-FPh   2-FPh     OH                                                       205 2-FPh   2,4-Cl.sub.2Ph                                                                           OH                                                       __________________________________________________________________________      ##STR84##                                                                

                                      TABLE 2                                      __________________________________________________________________________      ##STR85##                                                                     No.  R.sup.1   R.sup.2                                                         __________________________________________________________________________      1a  n-C.sub.3 H.sub.7                                                                        phenyl                                                           2a  n-C.sub.3 H.sub.7                                                                        4-ClPh                                                           3a  n-C.sub.3 H.sub.7                                                                        4-FPh                                                            4a  n-C.sub.3 H.sub.7                                                                        4-FPh                                                            5a  n-C.sub.3 H.sub.7                                                                        4-MePh                                                           6a  n-C.sub.3 H.sub.7                                                                        2-ClPh                                                           7a  n-C.sub.3 H.sub.7                                                                        2-FPh                                                            8a  n-C.sub.3 H.sub.7                                                                        2,4-Cl.sub.2 Ph                                                  9a  n-C.sub.3 H.sub.7                                                                        3-pyridine                                                      10a  n-C.sub.3 H.sub.7                                                                        3-pyridine                                                      11a  n-C.sub.3 H.sub.7                                                                        3-pyridine                                                      12a  n-C.sub.3 H.sub.7                                                                        3-pyridine                                                      13a  n-C.sub.3 H.sub.7                                                                        3-pyridine                                                      14a  n-C.sub.3 H.sub.7                                                                        4-pyridine                                                      15a  n-C.sub.3 H.sub.7                                                                        2-pyridine                                                      16a  n-C.sub.3 H.sub.7                                                                        1-naphthyl                                                      17a  n-C.sub.3 H.sub.7                                                                        2-naphthyl                                                      18a  n-C.sub.3 H.sub.7                                                                        4-biphenyl                                                      19a  n-Bu      phenyl                                                          20a  n-Bu      4-ClPh                                                          21a  n-Bu      4-FPh                                                           22a  n-Bu      4-MePh                                                          23a  n-Bu      2-ClPh                                                          24a  n-Bu      2-FPh                                                           25a  n-Bu      2,4-Cl.sub.2Ph                                                  26a  n-Bu      3-pyridine                                                      27a  t-Bu      Ph                                                              28a  t-Bu      4-ClPh                                                          29a  t-Bu      4-ClPh                                                          30a  t-Bu      4-ClPh                                                          31a  t-Bu      4-ClPh                                                          32a  t-Bu      4-ClPh                                                          33a  t-Bu      4-ClPh                                                          34a  t-Bu      4-FPh                                                           35a  t-Bu      4-FPh                                                           36a  t-Bu      4-MePh                                                          37a  t-Bu      2-ClPh                                                          38a  t-Bu      2-FPh                                                           39a  t-Bu      2,4-Cl.sub.2Ph                                                  40a  t-Bu      3-pyridine                                                      41a  t-Bu      3-pyridine                                                      42a  t-Bu      cyclohexyl                                                      43a  t-Bu      cyclohexyl                                                      44a  t-Bu      cyclohexyl                                                      45a  t-Bu      cyclohexyl                                                      46a  t-Bu      cyclohexyl                                                      47a  t-Bu      cyclohexyl                                                      48a  t-Bu      cyclohexyl                                                      49a  n-pentyl  Ph                                                              50a  n-pentyl  4-ClPh                                                          51a  n-pentyl  4-FPh                                                           52a  n-pentyl  4-MePh                                                          53a  n-pentyl  2-ClPh                                                          54a  n-pentyl  2-FPh                                                           55a  n-pentyl  2,4-Cl.sub.2PH                                                  56a  n-pentyl  3-pyridine                                                      57a  n-pentyl  3-pyridine                                                      58a  n-pentyl  3-pyridine                                                      59a  n-pentyl  3-pyridine                                                      60a  n-pentyl  3-pyridine                                                      61a  n-pentyl  3-pyridine                                                      62a                                                                                  ##STR86##                                                                               Ph                                                              63a                                                                                  ##STR87##                                                                               4-ClPh             bp 117-120° C./0.4 mbar               64a                                                                                  ##STR88##                                                                               4-FPh                                                           65a                                                                                  ##STR89##                                                                               4-MePh                                                          66a                                                                                  ##STR90##                                                                               2-ClPh                                                          67a                                                                                  ##STR91##                                                                               2-FPh                                                           68a                                                                                  ##STR92##                                                                               2,4-Cl.sub.2Ph                                                  69a                                                                                  ##STR93##                                                                               3-pyridine                                                      70a  n-hexyl   Ph                                                              71a  n-hexyl   4-ClPh                                                          72a  n-hexyl   4-FPh                                                           73a  n-hexyl   4-MePh                                                          74a  n-hexyl   2-ClPh                                                          75a  n-hexyl   2-FPh                                                           76a  n-hexyl   2,4-Cl.sub.2Ph                                                  77a  n-hexyl   3-pyridine                                                      78a                                                                                  ##STR94##                                                                               Ph                                                              79a                                                                                  ##STR95##                                                                               4-ClPh                                                          80a                                                                                  ##STR96##                                                                               4-FPh                                                           81a                                                                                  ##STR97##                                                                               4-MePh                                                          82a                                                                                  ##STR98##                                                                               2-ClPh                                                          83a                                                                                  ##STR99##                                                                               2-FPh                                                           84a                                                                                  ##STR100##                                                                              2,4-Cl.sub.2Ph                                                  85a                                                                                  ##STR101##                                                                              3-pyridine                                                      86a  Ph        Ph                                                              87a  Ph        4-ClPh                                                          88a  Ph        4-FPh                                                           89a  Ph        4-MePh                                                          90a  Ph        2-ClPh                                                          91a  Ph        2-FPh                                                           92a  Ph        2,4-Cl.sub.2Ph                                                  93a  Ph        3-pyridine         mp 94° C.                             94a  Ph        n-Bu                                                            95a  Ph        t-Bu                                                            96a  Ph        n-pentyl                                                        97a  Ph                                                                                        ##STR102##                                                     98a  Ph                                                                                        ##STR103##                                                     99a  Ph                                                                                        ##STR104##                                                     100a Ph                                                                                        ##STR105##                                                     101a Ph                                                                                        ##STR106##                                                     102a Ph                                                                                        ##STR107##                                                     103a Ph                                                                                        ##STR108##                                                     104a 4-ClPh                                                                                    ##STR109##                                                     105a Ph        n-hexyl                                                         106a Ph                                                                                        ##STR110##                                                     107a Ph                                                                                        ##STR111##                                                     108a Ph                                                                                        ##STR112##                                                     109a Ph                                                                                        ##STR113##                                                     110a Ph                                                                                        ##STR114##                                                     111a Ph                                                                                        ##STR115##                                                     112a Ph        CH.sub.2CH.sub.2                                                113a Ph                                                                                        ##STR116##                                                     114a Ph        CH.sub.2CH.sub.2Ph                                              115a Ph        CH.sub.2CH.sub.2Ph                                              116a Ph        CH.sub.2CH.sub.2Ph                                              117a Ph        CH.sub.2CH.sub.2Ph                                              118a Ph        CH.sub.2CH.sub.2Ph                                              119a Ph        CH.sub.2CH.sub.2Ph                                              120a Ph        CH.sub.2CH.sub.2Ph                                              121a Ph        CH.sub.2CH.sub.2Ph                                              122a 4-ClPh    Ph                                                              123a 4-ClPh    4-ClPh                                                          124a 4-ClPh    4-FPh                                                           125a 4-ClPh    4-FPh                                                           126a 4-ClPh    4-FPh                                                           127a 4-ClPh    4-FPh                                                           128a 4-ClPh    4-FPh                                                           129a 4-ClPh    4-FPh                                                           130a 4-ClPh    4-FPh                                                           131a 4-ClPh    4-FPh                                                           132a 4-ClPh    4-MePh                                                          133a 4-ClPh    2-ClPh                                                          134a 4-ClPh    2-FPh                                                           135a 4-ClPh    2,4-Cl.sub.2Ph                                                  136a 4-ClPh                                                                                    ##STR117##        bp 119-122° C./0.01 mbar              137a 4-ClPh                                                                                    ##STR118##                                                     138a 4-FPh     2-ClPh             bp 164-184° C./0.3 mbar               139a 4-ClPh    2,2-(CH.sub.3).sub.2 -n-propyl                                                                    bp 120° C./0.01 mbar                  140a 4-FPh     2,2-(CH.sub.3).sub.2 -n-propyl                                                                    bp 85° C./0.1 mbar                    141a 4-ClPh    CH.sub.2CH.sub.2CH(CH.sub.3).sub.2CH.sub.3                                                        bp 120° C./0.1 mbar                   142a 1,1-(CH.sub.3).sub.2 -n-ethyl                                                            CH.sub.2CH.sub.2CH(CH.sub.3)CH.sub.3                                                              bp 110-130° C./0.3 mbar               143a 1,1-(CH.sub.3).sub.2 -n-ethyl                                                            4-ClPh             bp 120° C./0.4 mbar                   144a 4-FPh     3-pyridine         bp 155° C./0.1 mbar                   145a 4-ClPh    4-FPh              mp 84-85.5° C.                        146a 4-ClPh    2,4-dichloro-Ph    mp 130.5-131.5° C.                    __________________________________________________________________________

Generally speaking, the novel compounds are extremely effective on a broad spectrum of phytopathogenic fungi, in particular those from the Ascomycetes and Basidiomycetes classes. Some of them have a systemic action and can be used as foliar and soil fungicides.

The fungicidal compounds are of particular interest for controlling a large number of fungi in various crops or their seeds, especially wheat, rye, barley, oats, rice, Indian corn, lawns, cotton, soybeans, coffee, sugar cane, fruit and ornamentals in horticulture and viticulture, and in vegetables such as cucumbers, beans and cucurbits.

The novel compounds are particularly useful for controlling the following plant diseases:

Erysiphe graminis in cereaIs.

Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits,

Podosphaera leucotricha in apples,

Uncinula necator in vines,

Puccinia species in cereals,

Rhizoctonia species in cotton and lawns,

Ustilago species in cereals and sugar cane,

Venturia inaequalis (scab) in apples,

Helminthosorium species in cereals,

Septoria nodorum in wheat.

Botrytis cinerea (gray mold) in strawberries and grapes,

Cercospora arachidicola in groundnuts,

Pseudocercosporella herpotrichoides in wheat and barley,

Pyricularia oryzae in rice,

Phytophthora infestans in potatoes and tomatoes,

Fusarium and Verticillium species in various plants,

Plasmopara viticola in grapes,

Alternaria species in vegetables and fruit.

The compounds are applied by spraying or dusting the plants with the active ingredients or treating the seeds of the plants with the active ingredients. They may be applied before or after infection of the plants or seeds by the fungi. Either the fungi themselves, or the plants, seeds, materials or soil to be protected against fungal attack are treated with a fungicidally effective amount of the active ingredient.

The novel substances can be converted into conventional formulations such as solutions, emulsions, suspensions, dusts, powders, pastes and granules. The application forms depend entirely on the purposes for which they are intended; they should at all events ensure a fine and uniform distribution of the active ingredient. The formulations are produced in known manner. for example by extending the active ingredient with solvents and/or carriers, with or without the use of emulsifiers and dispersants; if water is used as solvent, it is also possible to employ other organic solvents as auxiliary solvents. Suitable auxiliaries for this purpose are solvents such as aromatics (e.g., xylene), chlorinated aromatics (e.g., chlorobenzenes), paraffins (e.g. crude oil fractions), alcohols (e.g., methanol, butanol), ketones (e.g., cyclohexanone), amines (e.g., ethanolamine, dimethylformamide), and water; carriers such as ground natural minerals (e.g. kaolins, aluminas, talc and chalk and ground synthetic minerals (e.g., highly disperse silica and silicates); emulsifiers such as nonionic and anionic emulsifiers (e.g., polyoxyethyIene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates); and dispersants such as lignin-sulfite waste liquors and methylcellulose.

The fungicidal agents generally contain from 0.1 to 95, and preferably from 0.5 to 90, wt. % of active ingredient. The application rates are from 0.02 to 3 kg or more of active ingredient per hectare, depending on the type of effect desired. The novel compounds may also be used for protecting materials (wood), for example against Paecilomyces variotii,

When the active ingredients are used for treating seed, amounts of from 0.001 to 50, and preferably from 0.01 to 10, g per kg of seed are usually employed.

The agents and the ready-to-use formulations prepared from them, such as solutions, emulsions, suspensions, powders, dusts. Pastes and granules, are applied in conventional manner, for example by spraying, atomizing, dusting, scattering, dressing or watering.

Examples of formulations are given below.

I. 90 parts by weight of compound no. 109 (Table 1) is mixed with 10 parts by weight of N-methyl-α-pyrrolidone. A mixture is obtained which is suitable for application in the form of very fine drops.

II. 20 parts by weight of compound no. 136 is dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzene-sulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into water and uniformly distributing it therein, an aqueous dispersion is obtained.

III. 20 parts by weight of compound no. 139 is dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 40 moles of ethylene oxide and mole of castor oil. By pouring the solution into water and finely distributing it therein, an aqueous dispersion is obtained.

IV. 20 parts by weight of compound no. 159 is dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point between 210° and 280° C., and 10 parts by weight of the adduct of 40 moles of ethylene oxide and i mole of castor oil. By pouring the solution into water and uniformly distributing it therein, an aqueous dispersion is obtained.

V. 80 parts by weight of compound no. 168 is well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-α-sulfonic acid. 10 parts by weight of the sodium salt of a lignin-suIfonic acid obtained from a sulfite waste liquor and 7 parts by weight of powdered silica gel. and triturated in a hammer mill. By uniformly distributing the mixture in water, a spray liquor is obtained.

VI. 3 parts by weight of compound no. 174 is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing 3% by weight of the active ingredient.

VII. 30 parts by weight of compound no. 109 is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingredient is obtained having good adherence.

VIII. 40 parts by weight of compound no. 136 is intimately mixed with 10 parts by weight of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water to give a stable aqueous dispersion. Dilution in water gives an aqueous dispersion.

IX. 20 parts by weight of compound no. 139 is intimately mixed with 2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of a fatty alcohol polyglycoI ether, 2 parts by weight of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil. A stable oily dispersion is obtained.

In these application forms, the agents according to the invention may also be present together with other active ingredients, for example herbicides, insecticides growth regulators, and fungicides, and may furthermore be mixed and applied together with fertilizers. Admixture with other fungicides frequently results in an increase in the fungicidal spectrum.

Use example

Action on Pyricularia oryzae (protective)

Leaves of pot-grown rice seedlings of the "Bahia" variety were sprayed to runoff with aqueous emulsions containing (dry basis) 80% of active ingredients and 20% of emulsifier, and inoculated 24 hours later with an aqueous spore suspension of Pyricularia oryzae. The plants were then set up in climatic cabinets at from 22° to 24° C. and a relative humidity of 95 to 99%. The extent of fungus spread was determined after 6 days. The results show that active ingredients 109, 136, 139, 159, 168 and 174, applied as 0.05 wt. % spray liquors, have a good fungicidal action (90%). 

We claim:
 1. A compound of the formula I ##STR119## wherein R¹ and R² are each phenyl, biphenylyl, or naphthyl and these radicals may be mono- to tri-substituted by halogen, nitro, phenoxy, amino, haloalkyl, alkyl or alkoxy, each of 1 to 4 carbon atoms, or are each C₁ -C₈ -alkyl which is unsubstituted or substituted by phenyl, halophenyl or C₁ -C₄ -alkylphenyl, R³ is a radical OR⁴, where R⁴ is hydrogen, C₁ -C₆ -halobenzoyl alkyl, ##STR120## benzoyl or halobenzoyl or R₃ is a radical NHR⁵, where R⁵ is hydrogen, phenyl, nitrophenyl, or the carbamide group CONH₂.
 2. Compounds of the formula I as set forth in claim 1, where R² is 2,2-dimethylpropyl, R³ is OH, and R¹ is phenyl which is unsubstituted or substituted by one or two identical or different radicals selected from the group consisting of fluoro, chloro, bromo and methyl.
 3. A fungicidal composition containing a carrier and a fungicidally effective amount of a 1-azabutadiene of the formula I ##STR121## where R¹ and R² are each phenyl, biphenyly, or naphthyl and these radicals may be mono- to tri-substituted by halogen, nitro, phenoxy, amino, haloalkyl, alkyl or alkoxy, each of 1 to 4 carbon atoms, or are each C₁ -C₈ -alkyl which is unsubstituted or substituted by phenyl, halophenyl or C₁ -C₄ -alkylphenyl, R³ is a radical OR⁴, where R⁴ is hydrogen, C₁ -C₆ -halobenzoyl, alkyl, ##STR122## benzoyl or halobenzoyl or R₃ is a radical NHR⁵, where R⁵ is hydrogen, phenyl, nitrophenyl, or the carbamide group CONH₂.
 4. A compound of the formula I as set forth in claim 1, where R¹ is phenyl, R² is 3,3-dimethylbutyl and R³ is acetyloxy.
 5. A compound of the formula I as set forth in claim 1, where R¹ is 4-chlorophenyl, R² is 2,2-dimethylpropyl and R³ is OH.
 6. A compound of the formula I as set forth in claim 1, where R¹ is 4-chlorophenyl, R² is 2,2-dimethylpropyl and R³ is acetyloxy.
 7. A compound of the formula I ##STR123## wherein R¹ is phenyl, biphenylyl, or naphthyl, and these radicals may be mono- to tri-substituted by halogen, nitro, phenoxy, amino, haloalkyl, alkyl or alkoxy, each of 1 to 4 carbon atoms, or is C₁ -C₈ -alkyl which is unsubstituted or substituted by phenyl, halophenhyl or C₁ -C₄ -alkylphenyl; R² is biphenylyl which may be mono-to tri-substituted by halogen, nitro, phenoxy, amino, haloalkyl, alkyl or alkoxy, each of 1 to 4 carbon atoms, or is phenyl substituted by 1 to 3 groups selected from halogen, nitro, phenoxy, amino, haloalkyl, or alkoxy, each of 1 to 4 carbon atoms, or is naphthyl which may be mono- to tri-substituted by halogen, nitro, phenoxy, amino, haloalkyl, alkyl or alkoxy, each of 1 to 4 carbon atoms, or is C₁ -C₈ -alkly which is unsubstituted or substituted by phenyl, halophenyl or C₁ -C₄ -alkylphenyl; and R³ is phenyl, halophenyl, or C₁ -C₄ -alkylphenyl.
 8. A fungicidal composition containing a carrier and a fungicidally effective amount of a compound according to claim
 7. 